Process for producing nitrobenzene

ABSTRACT

The present invention relates to a process for the continuous production of nitrobenzene by the nitration of benzene with nitric acid and sulphuric acid under adiabatic conditions, not the entire production plant being shut down during a production stop, but the production plant being entirely or at least partly operated in recirculation mode. The invention further relates to a plant for producing nitrobenzene and to a method for operating a plant for producing nitrobenzene.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a national stage application under 35 U.S.C. § 371of PCT/EP2015/063924, filed Jun. 22, 2015, which claims the benefit ofEuropean Application No. 14173583.7, filed Jun. 24, 2014, both of whichare incorporated by reference herein.

FIELD

The present invention relates to a process for continuously preparingnitrobenzene by nitrating benzene with a mixture of nitric acid andsulfuric acid, in which, during a production shutdown, rather thanrunning the whole production plant down, the production plant is runwholly or at least partly in circulation. The present invention furtherrelates to a plant for preparation of nitrobenzene and to a method ofoperating a plant for preparation of nitrobenzene.

BACKGROUND

Nitrobenzene is an important intermediate in the chemical industry whichis required particularly for preparation of aniline and hence also forpreparation of the di- and polyisocyanates of the diphenylmethane seriesand the polyurethanes based thereon.

The nitration of benzene with nitric acid to give a crude nitrobenzenehas already been the subject of numerous publications and patentapplications. The processes that are standard nowadays correspondessentially to the concept of adiabatic nitration of benzene by amixture of sulfuric acid and nitric acid, which is generally referred toas mixed acid. Such a process was claimed for the first time in U.S.Pat. No. 2,256,999 and is described in current embodiments, for example,in EP 0 436 443 B1, EP 0 771 783 B1 and U.S. Pat. No. 6,562,247 B2. Itis a particular feature of the processes with an adiabatic reactionregime that no technical measures are taken to supply or remove heat toor from the reaction mixture.

Isothermal processes for nitration of benzene with mixed acid are alsoknown, as described, for example, in EP 0 156 199 B1.

Also known are processes, for example from U.S. Pat. No. 2,739,174 orU.S. Pat. No. 3,780,116, for the nitration of benzene that do notrequire the use of sulfuric acid.

In principle, gas phase processes for nitration of benzene with nitricacid or nitrogen oxides are also possible, but the yields achievablethereby at the present time are still low (EP 0 078 247 B1, EP 0 552 130B1).

A common factor to all these processes is that the reaction productformed at first is a crude nitrobenzene typically containing, asimpurities, nitric acid and—if nitration has been effected with mixedacid-sulfuric acid, water, benzene and, as organic impurities,dinitrobenzene, nitrated oxidation products of benzene, especiallynitrated phenols (nitrophenols). The crude nitrobenzene may also containorganic compounds formed from the compounds that were present asimpurities in the benzene used (WO 2008/148608 A1). In addition, thecrude nitrobenzene often also contains metal salts that may be presentin dissolved form in the acid residues or in the crude nitrobenzene (DE10 2007 059 513 A1). These impurities are undesirable since they canadversely affect downstream processes in which nitrobenzene is used, forexample the preparation of aniline. Suitable work processes whichinclude wash and distillation stages are described, for example, in U.S.Pat. No. 6,288,289 B1, EP 1 593 654 A1, EP 1 816 117 B1 and WO2011/021057 A1.

The quality of a reaction process for preparation of nitrobenzene isthus defined firstly by the content of unwanted secondary components andimpurities in the crude product that arise from improper conduct of thereaction. Secondly, the quality of a reaction process is defined in thatthe entire process can be operated without technical production outageor problems that necessitate intervention in the process, and thatlosses of feedstocks are prevented or at least minimized.

Such problems can occur, for example, in the startup and shutdown of thenitration reaction. Problems of this kind may, for example, be thatsolids are formed that lead to caking and blockage in the equipment(nitration tank, heat exchangers, conduits, etc.). A furtherdisadvantage is that, in the event that inspection, maintenance, repairand cleaning operations are necessary on or in a reactor or anotherplant section, it is regularly necessary always to switch off all plantsections since the process steps build on one another and hence alwaysproceed successively. As a result, it is necessary to empty the entireplant, which leads to a considerable amount of reject material.Furthermore, energy has to be expended in order to bring reactors andplant sections back to the respective operating temperatures. Suchproduction shutdowns for plant inspections, repair and cleaning measuresor shortfalls of raw material or auxiliary that occur, whether plannedor unplanned, are recurrent plant states which have a considerableinfluence on the economic operation of a plant or process that workscontinuously.

Although the prior art processes described succeed in preparingnitrobenzene with a high yield and without loss of quality in the endproducts, the only processes described are in the normal state ofoperation. Production shutdowns for plant inspections and repair andcleaning measures or, for example, shortage of raw material or auxiliaryare not taken into account. At the same time, production shutdowns,planned or unplanned, are recurrent plant states which have aconsiderable influence on the economic operation of a continuouslyoperating plant.

Such a production shutdown may be an inspection shutdown which isplanned in advance, for which purpose the plant is run down, the energysupplies are switched off and typically all plant sections that are tobe inspected are opened and cleaned for the purpose of examination. Suchan inspection may take one or more weeks. After the inspection hasended, the production plant is closed, optionally inertized and providedwith auxiliaries and, once the appropriate energy sources and rawmaterials are available, started up again. However, a productionshutdown is not necessarily associated with opening or anothermechanical intervention into a reactor or another apparatus in theplant, but may also be connected to the shutdown and restart of theproduction plant for various other reasons, for example in the event ofoutage of the raw material supply. In such a case, the plant istypically run in part-load operation and, in the worst case, when thelogistical supply chain is interrupted, has to be shut down.Furthermore, production shutdowns may be forced by requirements formaintenance, cleaning or repair in the production plant. Shutdowns herein the nitrobenzene process are typically described as short whenproduction is interrupted for up to one day. It is a feature of allthese production shutdowns in practice that there are losses ofproduction, and that, on restarting of the plant, for example wheninertization is necessary, nitrogen is consumed or, in the heating ofthe plant or the feedstocks, forms of energy such as steam and power arerequired.

The person skilled in the art is aware that an industrial processoperated semicontinuously or continuously proceeding from a productionplant in operation cannot be switched instantaneously to a productionshutdown, but has to be run down in a controlled manner beforehand. Thisis also the case for a plant outage in the event of an accident. Inorder to be able to produce again after the production shutdown, theplant has to be run back up to the process parameters before theproduction shutdown. Reactants and apparatuses have to be heated up,apparatuses may have to be inertized, and the loading of the apparatuseswith the reactants is gradually increased to the desired target value.During this startup phase, there is thus still loss of productionvolume, and a disproportionate amount of energy has to be expended inorder to prepare the cooled plant for startup and then to run it up tothe desired target value with observation of all operationally relevantparameters as well.

What would thus be desirable would be a process for preparingnitrobenzene in which simple measures enable optimization of productionshutdowns in the operation of the nitrobenzene preparation process interms of time taken, energy consumption, auxiliary and raw materialconsumption and/or reduction in wastes. This would lead to a notinconsiderable degree of improvement in productivity or economicviability of a continuously operated process or a correspondingproduction plant.

SUMMARY OF THE INVENTION

It has been found that, surprisingly, this object is achieved for anitrobenzene preparation process when (expressed in simplified form andwithout restriction thereto), during a brief shutdown, as many plantsections as possible are put in circulation mode (“on standby”), inorder to be able to start up the overall plant again immediately afterthe measure. It has also been found that, surprisingly, the energyconsumption in a plant put in circulation mode for 1 hour for up to 1day is sometimes smaller than completely shutting down the plant for oneday and then starting it up again. By means of a controlled circulationmode in the plant sections that are not affected by the brief shutdown,various advantages are implemented, as is still to be elucidated indetail further down.

The present invention therefore provides the following:

A process, preferably operated adiabatically, for preparingnitrobenzene, comprising the steps of

-   (I) nitrating benzene with nitric acid in sulfuric acid to form    nitrobenzene in a reactor, with introduction of benzene with a mass    flow rate of m₁, nitric acid with a mass flow rate of m₂ and    sulfuric acid with a mass flow rate of m₃ into the reactor;-   (II) separating the phases of the reaction mixture from step (I) in    a phase separation apparatus into an aqueous sulfuric    acid-containing phase and an organic nitrobenzene-containing phase;    and optionally (and preferably) steps (III) to (VII):-   (III) concentrating the aqueous phase obtained in step (II) by    evaporating water in an evaporation apparatus (called the “flash    evaporator”) to give an aqueous sulfuric acid-containing phase    having elevated sulfuric acid concentration, with recycling of the    concentrated sulfuric acid-containing aqueous phase via a sulfuric    acid tank into step (I) and use thereof as a constituent of mass    flow m₃;-   (IV) washing the organic nitrobenzene-containing phase obtained in    step (II) in at least two stages and separating off the aqueous    phase after each stage, using a wash vessel having a phase    separation unit or a wash vessel and a separate phase separation    apparatus in each stage,-   (V) distilling, preferably rectifying, the organic    nitrobenzene-containing phase obtained in the last stage of    step (IV) in a distillation apparatus,-   (VI) working up the wastewater from the first wash stage of step    (IV), comprising collecting the wastewater in a wastewater    collection vessel and cleaning this wastewater in an apparatus for    distillation or stripping,-   (VII) working up the wastewater from the second wash stage of step    (IV), comprising collecting the wastewater in a wastewater    collection vessel and cleaning this wastewater in an apparatus for    distillation or stripping, where the apparatus for distillation or    stripping may be connected up- and/or downstream of an apparatus for    thermal pressure decomposition, wherein

in the event of shutdown of one or more plant sections from steps (I) to(VII), if they are conducted, the mass flow m₁ and the mass flow m₂ arereduced to zero and, in at least one of the plant sections that has notbeen shut down, the output stream is used again as input stream for therespective plant section or an upstream plant section.

The present invention further provides a plant for preparation ofnitrobenzene, as is still to be described in detail further down, andwhich is suitable for the performance of the process of the invention.

Finally, the present invention provides a method of operating a plantfor preparation of nitrobenzene, which is still to be described indetail further down.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an embodiment with three wash stages with processstreams in regular operation, without the optional thermal pressuredecomposition.

FIG. 2 illustrates an embodiment of the invention circulation mode inwhich (IV) and (V) operate together such that the output stream from(IV) forms the input stream for (V) and the output stream from (V) formsthe input stream for (IV).

DETAILED DESCRIPTION

The “shutdown” of a plant section means the stoppage thereof, such thatan inspection, repair, maintenance or cleaning measure can be conductedin the plant section. The present invention is thus concerned with thoseproduction shutdowns which can be described as “brief shutdowns” forinspection, repair, cleaning or maintenance purposes in sections of theplant or, for example, as a result of a time-limited lack of feedstocksor auxiliaries. The present invention makes it possible to implementsuch a measure in a plant section without having to shut down the entireproduction plant. Instead, the present invention enables operation ofplant sections not affected by the inspection, repair, maintenance orcleaning measure, or of the corresponding process steps, in “circulationmode”. Thus, the complete shutdown of the plant is restricted toexceptional (rare) cases, for instance a complete plant inspection.According to the invention, the term “shutdown” accordingly encompasses,in the case of presence of m plant sections within the meaning of thepresent invention (in this regard, see also the paragraph whichfollows), where m is a natural number, the shutdown of a maximum of m−1of these plant sections. According to the invention, at least one plantsection is thus not “shut down” (i.e. “completely stopped”). Preferably,the present invention is concerned with the case of shutdown of 1 to 2plant sections, more preferably of 1 plant section. According to theinvention, therefore, in the case of shutdown of a plant section (or twoor more plant sections, but not all plant sections), the formation offurther product is always interrupted (since the mass flow rates m₁ andm₂ are being reduced to zero and, therefore, no further product can beproduced). Also encompassed by the invention, however, is the case thatthe reactor from step (I) is being operated in circulation mode (in thisregard, see also the paragraph which follows) and another plant sectionwithin the meaning of the above definition is being shut down.“Circulation mode” is understood in the context of this invention tomean that the output stream from a plant section is used as input streamfor this plant section or another plant section connected directly orindirectly (i.e. with further plant sections in between) upstream of theplant section in question. In this context, “plant section” means theplant section corresponding to the respective step (I) to (V), if theyare conducted, in a plant for preparation of nitrobenzene by the processof the invention.

For example, the plant section from step (I) comprises “a reactor”, thisterm also encompassing embodiments in which two or more reactors (forexample a cascade of two or more reactors connected in series) are used(in other words, the word “a” in this connection and in connection withother apparatuses of other plant sections as well should be regarded asthe indeterminate article and not to mean the number “one”). Reactorsconnected in parallel or in series are known in the prior art in thepreparation of nitrobenzene as well, and can also bring advantages inparticular dimensions and operational characteristics. A plant sectionmay thus comprise two or more apparatuses, i.e. different apparatuses(e.g. wash vessel and phase separation apparatus in step (IV)). Theplant section from step (II) comprises a phase separation apparatus, theplant section from step (III) an evaporation apparatus, the plantsection from step (IV) comprises, as well as the crude nitrobenzene tankfor each wash stage, a wash vessel (either with integrated unit forphase separation or followed by a separate phase separation apparatus),and the plant section from step (V) a distillation apparatus. It will beappreciated that the plant sections, as well as the apparatuses detailedexplicitly above, may also include peripheral equipment, for examplepumps, heat exchangers and the like.

The circulation mode can also be established over several apparatuses ofa plant section. For example, the output stream from the last apparatusof a plurality of apparatuses connected in series in a plant section maybe used as input stream for the first apparatus of the apparatusesconnected in series in this plant section. It is also possible to applythe circulation mode only to a portion of the apparatuses of a plantsection, for example when the output stream from the last apparatus of aplurality of apparatuses connected in series in a plant section isrecycled not into the first but into a further apparatus of this plantsection.

The circulation mode can also be established over two or more plantsections. For example, the output stream from the last apparatus of aplant section, for example the nitrobenzene stream obtained in thedistillation in step (V), can be used as input stream for the firstapparatus of an upstream plant section, for example the wash in step(IV), in which case the circulation mode is established in that theoutput stream from the distillation mentioned by way of example servesas input stream for the wash.

The stopping of m₁ and m₂, i.e. the mass flows of benzene and nitricacid into the reactor from step (I), ensures that, during theinterruption which, as described above, is implemented for the purposeof inspection, maintenance, repair and/or cleaning of a section of theproduction plant or is caused by a shortage of raw material(s) and/orauxiliary/auxiliaries, the reaction in step (I) does not continue totake place. This, and the use of the output stream from at least oneuninterrupted step and corresponding plant section as input stream forthe respective step and corresponding plant section or an upstream plantsection, ensures that the steps and corresponding plant sections areeach run in circulation.

Embodiments of the process of the invention are described hereinafter.They may be combined with one another as desired unless the opposite isclear from the context.

The individual steps of the process of the invention are preferablyconducted within a continuous operation.

It is particularly preferable that the process of the invention alsocomprises steps (III), (IV), (V), (VI) and (VII).

The overall process of nitrobenzene preparation can be subdivided inconceptual terms as follows:

-   1.) nitration reaction (step (I) and corresponding plant section)    with phase separation (step (II) and corresponding plant section)    and concentration of the sulfuric acid (step (III) and corresponding    plant section),-   2.) washes (preferably acidic, alkaline and neutral wash; step (IV)    and corresponding plant section),-   3.) distillation (step (V) and corresponding plant section) and-   4.) optionally (and preferably) acidic wastewater workup (step (VI)    and corresponding plant section) and-   5.) optionally (and preferably) alkaline wastewater workup    (step (VII) and corresponding plant section).

Preferably, step (IV) comprises the steps of

-   (IVa) washing the organic nitrobenzene-containing phase obtained in    step (II) in at least one acidic wash, then separating the phases    into an aqueous phase and an organic nitrobenzene-containing phase    (1st wash stage);-   (IVb) washing the organic phase obtained in step (IVa) in at least    one alkaline wash with an aqueous solution of a base selected from    the group consisting of sodium hydroxide, sodium carbonate and    sodium hydrogencarbonate, then separating the phases into an aqueous    phase and an organic nitrobenzene-containing phase (2nd wash stage);-   (IVc) washing the organic phase obtained in step (IVb) in at least    one neutral wash, preferably two to four neutral washes, more    preferably two or three neutral washes, most preferably two neutral    washes, with water, then separating the phases into an aqueous phase    and an organic nitrobenzene-containing phase (3rd wash stage).

In a preferred embodiment, the process of the invention thereforecomprises the steps of

-   (I) nitrating benzene with mixtures of nitric acid and sulfuric acid    to form nitrobenzene in a reactor, with introduction of benzene with    a mass flow rate of m₁ and a mixture of nitric acid (mass flow rate    of m₂) and sulfuric acid (mass flow rate of m₃) into the reactor;-   (II) separating the phases of the reaction mixture from step (I) in    a phase separation apparatus into an aqueous phase and an organic    nitrobenzene-containing phase,-   (III) concentrating the sulfuric acid-containing aqueous phase from    step (II) in an evaporation apparatus to give an aqueous sulfuric    acid-containing phase having elevated sulfuric acid concentration,    with recycling of the concentrated sulfuric acid-containing aqueous    phase via a sulfuric acid tank into step (I) and use thereof as a    constituent of mass flow m₃;-   (IV) washing the organic nitrobenzene-containing phase obtained in    step (II) in at least two stages, using a wash vessel having a phase    separation unit or a wash vessel and a separate phase separation    apparatus in each stage, comprising    -   (IVa) washing the organic nitrobenzene-containing phase obtained        in step (II) in at least one wash, preferably one or two washes,        more preferably one wash (called “acidic wash(es)”), then        separating the phases into an aqueous phase and an organic        nitrobenzene-containing phase,    -   (IVb) washing the organic nitrobenzene-containing phase obtained        in step (IVa) in at least one alkaline wash, preferably one or        two alkaline washes, more preferably one alkaline wash, with an        aqueous solution of a base selected from the group consisting of    -   sodium hydroxide, sodium carbonate and sodium hydrogencarbonate,    -   then separating the phases into an aqueous phase and an organic        nitrobenzene-containing phase,    -   (IVc) washing the organic nitrobenzene-containing phase obtained        in step (IVb) in at least one neutral wash, preferably two to        four neutral washes, more preferably two or three neutral        washes, most preferably two neutral washes, with water, then        separating the phases into an aqueous phase and an organic        nitrobenzene-containing phase,    -   (V) distilling, preferably rectifying, the organic        nitrobenzene-containing phase obtained in step (IVc) to obtain        purified nitrobenzene,    -   (VI) working up the wastewater obtained in step (IVa),        comprising collecting the wastewater in a wastewater collection        vessel and cleaning this wastewater in an apparatus for        distillation or stripping, and    -   (VII) working up the wastewater from step (IVb), comprising        collecting the wastewater in a wastewater collection vessel and        cleaning this wastewater in an apparatus for distillation or        stripping, where the apparatus for distillation or stripping may        be connected up- and/or downstream of an apparatus for thermal        pressure decomposition,

wherein, in the event of shutdown of one or more plant sections fromsteps (I) to (VII), the mass flow m₁ and the mass flow m₂ are reduced tozero and, in at least one of the plant sections that has not been shutdown, the output stream is used again as input stream for the respectiveplant section or an upstream plant section.

Thermal pressure decomposition is understood here to mean a process forworkup of alkaline wastewater in which organic impurities are decomposedunder the action of elevated pressure and elevated temperature. Suitableprocesses are known to those skilled in the art and are described, forexample, in EP 1 593 654 B1. In the context of the present invention, itis especially preferable to heat the alkaline wastewater (optionallypretreated in the apparatus for distillation or stripping), withexclusion of oxygen, to temperatures of 150° C. to 500° C. under anabsolute pressure of 50 bar to 350 bar.

The appended drawing FIG. 1 shows an embodiment with three wash stages(without the optional thermal pressure decomposition) with processstreams in regular operation:

Benzene (1), nitric acid (2) and sulfuric acid (3) are converted in areactor (1000). The process product of this step (I), stream 4, isseparated in a phase separation apparatus (2000) into an aqueous phase(5) and an organic nitrobenzene-containing phase (7) (step (II)). Theaqueous phase (5) consisting essentially of dilute sulfuric acid isconcentrated in an evaporation apparatus (3000) (step (III)). Theconcentrated sulfuric acid-containing phase thus obtained is recycledvia a sulfuric acid tank (4000) into the reactor (1000) from step (I)and used as a constituent of mass flow m₃. The organic phase (7)obtained in step (II) is fed via a crude nitrobenzene tank (5000) to theindividual wash stages (5010-“acidic wash”; 5020-“alkaline wash”;5030-“neutral wash”), without showing the wash liquid streams suppliedfor the sake of simplicity. This gives the wastewater streams 8, 10 and12 and the washed organic nitrobenzene-containing phase 13 (step (IV)with component steps (IVa), (IVb) and (IVc)). The organic phase 13 ispurified in a distillation apparatus (6000) (step (V)), drawing off lowboilers (essentially unconverted benzene) overhead (stream 15) andnitrobenzene at the bottom (stream 14). This low boiler removal may befollowed by a further distillative purification stage (not shown) inwhich stream 14 is drawn off overhead or as a sidestream for removal ofhigh-boiling impurities.

The wastewater 8 from the first wash stage (IVa) is fed (stream 16) viaa wastewater collecting vessel (7010) to a purifying apparatus (8010),giving cleaned wastewater (17) (step (VI)). This apparatus 8010 is anapparatus for distillation or stripping. The wastewater 10 from thesecond wash stage (IVb) is fed (stream 18) via a wastewater collectingvessel (7020) to a purifying apparatus (8020), giving cleaned wastewater(19) (step (VII)). This apparatus 8020 is an apparatus for distillationor stripping. As already mentioned, the apparatus 8020 may be connectedup- and/or downstream of an apparatus for thermal pressure decomposition(not shown in FIG. 1). The wastewater 12 from the third wash stage (IVc)can, as known from the prior art, be disposed of or used further (notshown in FIG. 1).

The embodiment described relates especially to the case of a briefshutdown in production of 1 hour up to 1 day. The procedure of theinvention allows the production plant to be operated completely orpartly in circulation mode of individual plant sections. It isparticularly preferable here to conduct the circulation mode in eachcase over the above-defined constituents of the process for nitrobenzenepreparation. This means that (1) the nitration reaction with phaseseparation and concentration of the sulfuric acid, (2) the washes(acidic, alkaline and neutral wash), (3) the distillation and (4) acidicwastewater workup and (5) the alkaline wastewater workup are each put incirculation mode.

It is preferable here when, at least in steps (IV) and (V), the outputstreams are used again as input streams for the corresponding plantsections. This may also include use of the output stream from step (IV)again as input stream for this step, and running step (V) in exactly thesame way. Alternatively, however, it is also possible to operate steps(IV) and (V) together in circulation mode, meaning that the outputstream from step (IV) forms the input stream for step (V), and theoutput stream from step (V) forms the input stream for step (IV). Thisprocedure is shown in schematic and highly simplified form in FIG. 2.For example, the distillation can be put in circulation together withthe wash, in that the output from the distillation (nitrobenzene) goesinto the crude nitro tank and thence through the washes back to thedistillation.

In this context, it is especially preferable when, in the event ofinterruption of the process in at least one of steps (I) to (VII) (i.e.the shutdown of one or more plant sections from steps (I) to (VII)),with step (IV) comprising the abovementioned component steps, the outputstream in every other step (I) to (VII), i.e. every other step notaffected by the interruption, is used again as input stream for therespective plant section. In this way, the effects of the invention aremanifested to a particularly advantageous degree.

The present invention further provides a plant for preparation ofnitrobenzene, comprising the plant sections of:

-   (I) a reactor for nitration of benzene with a mixture of nitric acid    and sulfuric acid to form nitrobenzene,-   (II) a phase separation apparatus for phase separation of the    reaction mixture obtained in the reactor (I) into an aqueous    sulfuric acid-containing phase and an organic    nitrobenzene-containing phase, and optionally (and preferably) plant    sections (III) to (VII):-   (III) an evaporator (III.a) for concentration of the aqueous    sulfuric acid-containing phase and a sulfuric acid reservoir tank    (III.b) for accommodation of the concentrated aqueous sulfuric    acid-containing phase and the provision thereof for the reactor (I),-   (IV) a wash vessel with phase separation unit per wash stage or a    wash vessel and a separate phase separation apparatus per wash stage    for at least two-stage washing of the organic    nitrobenzene-containing phase from (II),-   (V) a distillation apparatus for purification of the organic    nitrobenzene-containing phase from (IV),-   (VI) a wastewater collection vessel and an apparatus for    distillation or stripping for collection and subsequent cleaning of    the wastewater from the first wash stage from (IV),-   (VII) a wastewater collection vessel and an apparatus for    distillation or stripping which may be connected up- and/or    downstream of an apparatus for thermal pressure decomposition, for    collection and subsequent cleaning of the wastewater from the second    wash stage from (IV),

wherein

the plant is configured such that, in the event of shutdown of one ormore plant sections (I) to (VII), if they are present, no furtherintroduction of benzene and nitric acid into the reactor (I) takes placeand, independently of one another or simultaneously, in at least oneplant section unaffected by the shutdown, the output stream is recycledand used as input stream for the respective plant section or an upstreamplant section. The configuration of the plant in such a way that “in theevent of shutdown of one or more plant sections (I) to (VII), if theyare present, no further introduction of benzene and nitric acid into thereactor (I) takes place” should be understood to mean that, prior to orsimultaneously with the shutdown of a plant section, the supply ofbenzene and nitric acid is interrupted; in other words, prior to orsimultaneously with the establishment of circulation mode in at leastone plant section unaffected by the shutdown, the supply of benzene andnitric acid is interrupted. In terms of apparatus, this can beimplemented in various ways, for example through the incorporation ofprocess control units which automatically interrupt the supply ofbenzene and nitric acid on shutdown of one or more plant sections (onsetting of one or more plant sections that are not to be shut down tocirculation mode). The setting-up of a barrier circuit which enables thesetting to circulation mode only in the event of interrupted supply ofbenzene and nitric acid is likewise conceivable. Suitable software andhardware products are commercially available and known to those skilledin the art. Any necessary programming and adaptation operations arewithin the routine duty which is customary to the person skilled in theart.

It will be apparent that this plant is especially configured to be ableto conduct the process of the invention therein. Thus, the advantagesand effects of the process of the invention also apply to the plant ofthe invention.

More preferably, plant section (IV) comprises:

-   (IVa) a wash vessel with phase separation unit or a wash vessel and    a separate phase separation apparatus for washing and subsequent    phase separation of the organic nitrobenzene-containing phase from    (II),-   (IVb) a wash vessel with phase separation unit or a wash vessel and    a separate phase separation apparatus for washing and subsequent    phase separation of the organic nitrobenzene-containing phase from    (IVa),-   (IVc) a wash vessel with phase separation unit or a wash vessel and    a separate phase separation apparatus for washing and subsequent    phase separation of the organic nitrobenzene-containing phase from    (IVb).

It is especially preferable here that, independently of one another orsimultaneously, the output mass flow in every other plant sectionunaffected by the interruption is recycled and used again as input massflow for the respective plant section or an upstream plant section.Thus, in the plant sections unaffected by the interruption, at least onecirculation mode is conducted.

Should two or more nitration reactor lines be operated in parallel, itis firstly possible to operate one reactor line in the circulation modeof the invention and to set the other reactor lines successively to thecirculation mode of the invention. Alternatively, however, it is alsopossible in the context of the present invention to transfer allnitration reactor lines simultaneously or essentially simultaneously tothe circulation mode of the invention. Likewise encompassed by theprocesses and the plant according to the present invention are cases inwhich 3 or 4 reactor lines go into 1 or 2 phase separation apparatuses,1 or 2 phase separation apparatuses go into 2 flash evaporators, and thesulfuric acid that flows away from the latter is optionally guided intoa sulfuric acid reservoir. The organic phase that emerges from the phaseseparation apparatus can be worked up, for example, in a single-linewash with distillation.

Examples of different circulation modes are listed hereinafter:

-   -   1.) In the nitration reaction with phase separation and        concentration of the sulfuric acid, consisting of nitrators with        sulfuric acid circulation pumps, phase separators, flash        evaporators with vacuum pumps and condensers and sulfuric acid        reservoir, the benzene stream and nitric acid stream are stopped        at the same time. The circulating sulfuric acid can then be        pumped under reaction starting conditions (preferably 101° C.)        by means of the sulfuric acid circulation pumps through the        nitrators, phase separation, flash evaporator (sulfuric acid        concentration) into the sulfuric acid reservoir and thence in a        circuit back to the nitrators for several hours.    -   2.) In the washes, consisting of a crude nitrobenzene tank and        an acidic, alkaline and neutral wash, the crude nitrobenzene        stream from the phase separation apparatus to the crude nitro        tank is interrupted. The washed crude nitrobenzene can then be        pumped from the neutral wash to the crude nitro tank, through        the acidic wash and alkaline wash and back to the neutral wash        in circulation for an indeterminate period. The wash water is        run in countercurrent into the neutral wash through the alkaline        wash to the alkaline wastewater workup. In the course of this,        the flow rate of the crude nitrobenzene from the crude        nitrobenzene tank to the acidic wash and of the wash water to        the neutral wash is reduced to minimal load.    -   3.) In the distillation, consisting of a heat exchanger,        nitrobenzene column with bottoms withdrawal of the nitrobenzene        end product and a natural circulation evaporator, vapor        condensers with vacuum pumps, vapor phase separation apparatus        and return benzene reservoir with pump, after the reaction has        been stopped, no further crude nitrobenzene occurs in the        washes. The bottoms output from the nitrobenzene column is sent        back to the crude nitrobenzene tank through the heat exchanger        and hence circulated through all the washes and through the        nitrobenzene column. The vapors obtained (benzene and water) are        condensed and separated in the vapor phase separation apparatus        into an aqueous phase and an organic phase. The        benzene-containing organic phase is likewise conducted to the        crude nitrobenzene tank. The aqueous phase is disposed of via        the acidic wash and the acidic wastewater workup (the vacuum        system remains in operation). The circulation mode can be        operated for an indefinite period.    -   4.) In the acidic wastewater workup, consisting of a wastewater        reservoir tank, a heat exchanger, a wastewater distillation with        condensation system, a wastewater cooler and outlet to the        acidic wash, after the nitration has been shut down, no further        acidic wastewater occurs. The wastewater distillation can be        operated with steam for an indefinite period, in which case the        acidic wastewater in the bottoms from the wastewater column is        put in circulation mode to the wastewater reservoir tank and the        vapors obtained are run to the acidic wash.    -   5.) In the alkaline wastewater workup, consisting of a        wastewater reservoir tank, a heat exchanger, a wastewater        distillation with condensation system and an outlet to a plant        for thermal pressure decomposition (TDZ), after the alkaline        wash has been shut down, no further alkaline wastewater occurs.        The wastewater distillation can be operated with steam for an        indefinite period, in which case the alkaline wastewater in the        bottoms from the wastewater column is put in circulation mode to        the wastewater reservoir tank and the vapors obtained are run to        the acidic wash. The TDZ, consisting of a wastewater reservoir        with high-pressure pump, heat exchanger, steam heater, dwell        tube and cooler, may be operated with steam for an indefinite        period, in which case the alkaline wastewater from the exit of        the TDZ is put in circulation mode to the wastewater reservoir.

These examples are of course merely representative of a multitude ofpossible circulation modes, the exact configuration of which depends onthe specific circumstances in a production plant and therefore cannot begeneralized. However, a feature common to all conceivable circulationmodes is that no product leaves the plant when the plant is a singlenitrobenzene line.

Should two or more nitrobenzene reactor lines be operated in parallel,it is possible but not obligatory for product to leave the plant when,for example, the plant is being run with partial load.

The present invention further provides a method of operating a plant forpreparation of nitrobenzene, comprising the plant sections of:

-   (I) a reactor for nitration of benzene with a mixture of nitric acid    and sulfuric acid to form nitrobenzene,-   (II) a phase separation apparatus for phase separation of the    reaction mixture obtained in the reactor (I) into an aqueous    sulfuric acid-containing phase and an organic    nitrobenzene-containing phase, and optionally (and preferably) plant    sections (III) to (VII):-   (III) an evaporator (III.a) for concentration of the aqueous    sulfuric acid-containing phase and a sulfuric acid reservoir tank    (III.b) for accommodation of the concentrated aqueous sulfuric    acid-containing phase and the provision thereof for the reactor (I),-   (IV) a wash vessel with phase separation unit per wash stage or a    wash vessel and a separate phase separation apparatus per wash stage    for at least two-stage washing of the organic    nitrobenzene-containing phase from (II), plant section (IV) more    preferably comprising the above-defined constituents (IVa), (IVb)    and (IVc),-   (V) a distillation apparatus for purification of the organic    nitrobenzene-containing phase from (IV),-   (VI) a wastewater collection vessel and an apparatus for    distillation or stripping for collection and subsequent cleaning of    the wastewater from the first wash stage from (IV),-   (VII) a wastewater collection vessel and an apparatus for    distillation or stripping which may be connected up- and/or    downstream of an apparatus for thermal pressure decomposition, for    collection and subsequent cleaning of the wastewater from the second    wash stage from (IV),

wherein shutdown of one or more plant sections (I) to (VII), if they arepresent, is accomplished by running through the following steps:

(i) stopping the supply of benzene and nitric acid and optionallysulfuric acid into the reactor (I);

(ii) running at least one plant section in such a way that the outputstream from the respective plant section is used as input stream for therespective plant section or an upstream plant section (circulationmode);

(iii) shutting down at least one plant section.

Especially preferably, the plant is the plant of the invention forpreparation of nitrobenzene.

In a preferred embodiment, this method of the invention comprises thefurther steps of:

(iv) optionally opening the at least one plant section shut down in step(iii);

(v) conducting a maintenance, cleaning, inspection and/or repairmeasure;

(vi) optionally closing and optionally inertizing the at least one plantsection from step (v);

(vii) starting up the at least one plant section from step (vi);

(viii) starting the supply of benzene and nitric acid into the reactor(I).

More preferably, every plant section which has not been run down (shutdown) is switched to circulation mode and hence the advantages andeffects of the present invention are advantageously achieved.

In a plant of the invention, the process of the invention can beconducted, for example, as follows:

In the first step, the input streams of benzene and nitric acid arestopped at the same time. The circulating sulfuric acid can then be sentunder reaction starting conditions (preferably 101° C.) by means of thesulfuric acid circulation pumps through the nitrators, phase separation,flash evaporator (sulfuric acid concentration) into the sulfuric acidreservoir and thence in a circuit back to the nitrators.

In the second step, once the washed crude nitrobenzene from the neutralwash is being conducted to the crude nitro tank, through the acidic washand alkaline wash and back to the neutral wash, the washes are put incirculation mode.

In the third step, the distillation is put in circulation mode togetherwith the washes.

In the fourth step, the acidic wastewater workup is put in circulationmode.

In the fifth step, the alkaline wastewater workup comprising wastewatercolumn and TDZ is put in circulation mode.

The plant section affected, for example, by a maintenance measure is rundown, emptied, cleaned and optionally opened for the pending measure.Then the maintenance measure is conducted and the plant section isclosed again, inertized and charged with auxiliaries and feed materials,and prepared for startup.

In order to start up the plant again, first the acidic wastewaterworkup, the washes with distillation and then the nitration is put intooperation. The alkaline wastewater workup is put in operation asrequired, since it is decoupled from the rest of the plant by means of abuffer tank (wastewater reservoir tank).

The restarting of the plant from circulation mode can be conducted, forexample, as follows:

-   -   1.) In the acidic wastewater workup, consisting of a wastewater        reservoir tank, a heat exchanger, a wastewater distillation with        condensation system, a wastewater cooler and outlet to the        acidic wash, after the nitration has been shut down, acidic        wastewater occurs again. The wastewater distillation is put in        operation by sending the acidic wastewater in the bottoms from        the wastewater column to the wastewater conduit.    -   2.) In the washes, consisting of a crude nitrobenzene tank and        an acidic, alkaline and neutral wash, the crude nitrobenzene        from the crude nitrobenzene tank is run into the acidic wash,        through the alkaline wash to the neutral wash. The crude        nitrobenzene leaving the neutral wash is sent to the        distillation. The wash water is run in countercurrent into the        neutral wash through the alkaline wash to the alkaline        wastewater workup. In the course of this, the flow rate of the        crude nitrobenzene from the crude nitrobenzene tank to the        acidic wash and of the wash water to the neutral wash is run up        to startup load.    -   3.) In the distillation, consisting of a heat exchanger,        nitrobenzene column with bottoms withdrawal of the nitrobenzene        end product and a natural circulation evaporator, vapor        condensers with vacuum pumps, vapor phase separation apparatus        and return benzene reservoir with pump, crude nitrobenzene        occurs again. The bottoms output from the nitrobenzene column is        sent through the heat exchanger to the end product tank. The        vapors obtained (benzene and water) are condensed and separated        in the vapor phase separation apparatus into an aqueous phase        and an organic phase. The benzene-containing organic phase is        conveyed to the return benzene tank. The aqueous phase continues        to be disposed of via the acidic wash and the acidic wastewater        workup.    -   4.) In the nitration reaction with phase separation and        concentration of the sulfuric acid, consisting of nitrators with        sulfuric acid circulation pumps, phase separation apparatus,        flash evaporator with vacuum pumps and condensers and sulfuric        acid reservoir, the circulating sulfuric acid continues to be        run back into the sulfuric acid reservoir through the nitrators,        phase separation and flash evaporator (sulfuric acid        concentration) under reaction starting conditions (preferably        101° C.) by means of the sulfuric acid circulation pumps. At the        same time, the benzene stream and nitric acid stream are        switched on. The crude nitrobenzene obtained in the phase        separation apparatus is fed to the crude nitrobenzene tank.    -   5.) In the alkaline wastewater workup, consisting of a        wastewater reservoir tank, a heat exchanger, a wastewater        distillation with condensation system and an outlet to a plant        for thermal pressure decomposition (TDZ), after the alkaline        wash has been started up, alkaline wastewater occurs again. The        alkaline wastewater in the bottoms from the wastewater column is        sent to the TDZ, and the vapors obtained continue to be run to        the acidic wash. The TDZ, consisting of wastewater reservoir        with high-pressure pump, heat exchanger, steam heater, dwell        tube and cooler, is then charged with stripped alkaline        wastewater and the output from the TDZ is sent to the wastewater        conduit.

The complete nitrobenzene plant is now running with reduced load(startup load) and can now be run up to the desired target production.

It is particularly preferable here to run up the production plant withreduced load, since the required temperature profiles for the nitration,washes, wastewater workup and distillation are otherwise not availablequickly enough, which could lead to incomplete nitration with increasedby-products and more difficult workup conditions.

The changeover to circulation mode can be conducted, for example, forthe nitration reaction with phase separation and concentration of thesulfuric acid, washes (crude nitrobenzene tank, acidic, alkaline andneutral wash), distillation and acidic wastewater workup and alkalinewastewater workup as follows:

The overall plant is run down in a first step (step a)) by stopping thebenzene feed and nitric acid feed to the nitration reactor. Circulatingsulfuric acid continues to circulate, and the crude nitrobenzene stillbeing formed in the nitration reactor is flushed into the phaseseparation apparatus. The phases are separated therein and residualcrude nitrobenzene is discharged to the crude nitrobenzene tank. In theflash evaporator, the circulating sulfuric acid is freed of residualorganics and kept at starting temperature (about 101° C.) by means ofsteam.

In step b) thereafter, the washes are switched to circulation mode, withthe crude nitrobenzene stream and the wash water stream being set tominimal load.

In step c) subsequently, the distillation is switched to circulationmode with retention of the vacuum.

In step d), after the reaction has been stopped, the acidic wastewaterworkup is switched to circulation mode.

In step e), after the washes from step b) have been shut down, thealkaline wastewater workup (including TDZ) is switched to circulationmode.

In step f), the plant section affected by the brief shutdown is brieflyshut down and the brief shutdown measure is conducted.

In step g), the plant section affected by the brief shutdown is madeready for operation again.

Subsequently, in step h), the overall plant is run up again fromcirculation mode and then brought to the desired target load.

The process of the invention gives rise to the following advantages:

-   -   i) Increase in productivity, because the availability of the        plant increases, since the time taken for the running down and        restarting of the plant for the production shutdown is greatly        minimized.    -   ii) Absence of capital costs for a greater plant capacity and        associated maintenance costs.    -   iii) It is possible to work with a smaller end product tank,        since less buffer volume is needed. As a result, lower capital        costs and maintenance costs for the end product tank also arise.    -   iv) In many cases, energy savings arise because there is no need        for the preparations required for the shut-down plant sections        that are needed for the restart, such as the heating of the        auxiliaries and feedstocks or the heating of the equipment etc.    -   v) Saving of auxiliaries such as steam condensate and nitrogen.    -   vi) The susceptibility of the pumps to need repair, specifically        in the nitration region, and of the vacuum pumps is improved        since the slip-ring seals thereof suffer from every restart of        the pumps when they are switched off in the event of a shutdown.        Thus, subsequent repairs are avoided, which again has a positive        effect on the productivity of the plant and maintenance costs.    -   vii) Avoidance of superfluous waste products, for example excess        benzene, excess nitric acid or nitric acid/sulfuric acid        mixtures, nitrated oxidation products of benzene and mixtures        with crude products or wastewater, which additionally have to be        purified, and which arise when the plant has to be subjected to        a complete new startup.

The success of the procedure of the invention is surprising to theperson skilled in the art because, in principle, in order to save energyand to be able to concentrate on the maintenance measures due in theproduction shutdown, the skilled person would be much more likely toshut down the entire plant, especially since additional capital costsfor recycling pipelines including pumps, retrofitting in the apparatusesand additional process control technology have to be accepted for theprocess of the invention and for the plant of the invention.

The present invention is to be illustrated hereinafter by examples.

EXAMPLES

Content figures in ppm or % are parts by mass based on the total mass ofthe respective material/stream. Analysis values, unless statedotherwise, have been determined by means of gas chromatography.

General Conditions for the Preparation of Nitrobenzene in a “Run-In”Production Plant

At a production load of 50 t/h of nitrobenzene, a sulfuric acid stream,a nitric acid stream, a fresh benzene stream and a return benzene streamwere metered into a nitration reactor. A 5% to 10% excess of benzene wasused, based on nitric acid. On completion of conversion of the nitricacid with the benzene to give nitrobenzene in an adiabatic reactionregime, the reaction product, now at about 130° C., was fed to a phaseseparation apparatus in which the reaction product separated into anorganic phase (=crude nitrobenzene, also containing benzene as well asnitrobenzene) and an aqueous phase (=waste acid, also containing smallproportions of nitrobenzene and benzene as well as sulfuric acid). Theaqueous phase comprising mainly sulfuric acid was subjected to a flashevaporation of water by abruptly lowering the pressure in theevaporator, and concentrated in this way. The concentrated sulfuric acidwas stored in the sulfuric acid tank for reuse. After being removed inthe phase separation apparatus, the crude nitrobenzene was cooled downto about 50° C. in the crude nitrobenzene cooling operation and sent tothe washing operation. This wash comprised an acidic wash stage, analkaline wash stage and a neutral wash stage.

The stream of purified crude nitrobenzene which has been substantiallyfreed of nitrophenols and salts and has been obtained in this way washeated up again and, in a distillation column, freed of water, benzeneand other low boilers which were removed overhead, giving dried purenitrobenzene. The condensed top product from the distillation column wasfed to a phase separation apparatus in which the top product separatedinto an organic phase (comprising benzene) and an aqueous phase. Theorganic phase was stored intermediately in a buffer tank and thence runback, as already described above, into the feed of the nitration reactorfor reaction. The power consumption of such a plant is about 890 kW/h.

The wastewater obtained in the alkaline wash was worked up as follows:

The wastewater from the alkaline wash was run into a settling tank inwhich undissolved benzene and nitrobenzene were separated out. 3.5tonnes per hour of alkaline wastewater which had a nitrobenzene contentof 2870 ppm, a benzene content of 409 ppm and a nitrophenols content of11 809 ppm and a pH of 12.8 (1.8% excess of NaOH compared to thestarting content of nitrophenols prior to the alkaline wash) wereconducted into a stripping column in order to remove benzene andnitrobenzene from this alkaline wastewater overhead by stripping withsteam. For this purpose, 500 kg/h of 6 bar steam were used. The pressurein the top of the column was 1.05 bar (absolute), and the temperaturewas 99.5° C. The top of the stripping column was equipped with avertical condenser in which the benzene- and nitrobenzene-containingvapors were condensed out, then recycled into the acidic wash. The moistoffgas at 99° C. from the stripping column was connected directly to thecondenser and was sprayed with acidic water at 30° C. from the acidwater tank. This prevents the possible deposition of ammonium nitrateand/or ammonium nitrite, which can form in the dry region of aconventional offgas conduit used for the separate conduction of theoffgas out of the condenser (the ammonium salts mentioned may form fromammonia and nitrogen oxides present in the alkaline wastewater). Theacidic water was fed to the acidic wash together with the condensedvapors. Any malfunction of the stripping column can be monitored, forexample, by means of redundant safety devices. After the stripping, analkaline wastewater that contained benzene only in a concentration of upto 10 ppm and nitrobenzene in a concentration of up to 10 ppm wasobtained. Subsequently, the alkaline wastewater thus treated was treatedin a plant for thermal pressure decomposition with a residence time of20 min, a temperature of 290° C. and an absolute pressure of 90 bar. Thewastewater that arose here was cooled down to 80° C. Thereafter, thewastewater was stripped with direct steam. In the bottoms from thestripping column, a stream of 4.0 tonnes per hour was obtained at anabsolute pressure of 1.02 bar, which contained essentially water,ammonia, carbon dioxide and organics. The top product was condensed andcooled down to 35° C. A purge stream of organics was discharged from thecondensate. 0.25 tonne per hour of the aqueous condensate streamdepleted of organics was recycled into the stripping column as reflux.The proportion of organics in the wastewater obtained, which was sent toa biological water treatment plant, was 4726 ppm. The ammonium contentin the wastewater was less than 87 ppm. There were no problems at allwith deposits in the region of the offgas from the stripping column.

Nitrobenzene prepared in this way typically has a purity of about 99.96%(GC), a residual benzene content of 0.0028% (GC), a 1,3-dinitrobenzenecontent of 0.0273% (GC) and a nitrophenol content of <5 ppm (HPLC). Inaddition, nitrobenzene has a water content of 0.0079% (determinedaccording to Karl Fischer).

Example 1 (Comparative Example): Brief Shutdown of a Production Plantwith Complete Stoppage of the Plant, Cleaning Measure and Restarting ofthe Plant

The brief shutdown of the plant served for conduction of cleaningoperations in the nitration region. For this purpose, the plant was rundown completely, i.e. nitration, washes, distillation, acid water workupand alkaline wastewater workup. The energy supplies were switched offduring the cleaning operations. After the cleaning operations, the plantwas started up again, for which it was necessary to inertize, fill andheat the entire plant beforehand.

Procedure for the Complete Stoppage of the Plant:

First, the nitration was shut down: The metering pumps for the inputstreams of benzene and nitric acid were switched off. The vapor from theflash evaporator was stopped 5 minutes after the benzene and nitric acidraw materials. The circulation of sulfuric acid continued for 1 houruntil all organics had been discharged from the nitration circuitconsisting of nitrators, phase separation apparatus, flash evaporatorand circulating sulfuric acid reservoir tank. Then the circulation ofsulfuric acid at 100° C. was interrupted by switching off thecirculation pump. The nitrators, the phase separation apparatus and theflash evaporator were left under standing sulfuric acid. The remainingcirculating sulfuric acid was in the sulfuric acid reservoir tank. Thetotal inventory of sulfuric acid was 74 tonnes. Simultaneously with thecirculation pump, the vacuum pump to the flash evaporator was switchedoff and the vacuum was broken with nitrogen. The nitration circuit wasthen at rest. Time taken 2 hours, without breaking the vacuum 1 hour.

Thereafter, the acid water workup was shut down by interrupting the feedof acidic wastewater from the acid water reservoir tank to the acidwater stripper. The steam to the acid water stripper and the bottomspump of the stripper were stopped. The acid water workup was then atrest. The time taken was 5 minutes.

Next, the washes were shut down by interrupting the crude nitrobenzenefeed from the crude nitrobenzene tank to the acidic wash. The crudenitrobenzene pathway through the acidic, alkaline and neutral wash wasstopped by stopping the delivery pumps for the crude nitrobenzeneupstream of the respective washes. The washes had an operatingtemperature of 48° C. and remained filled with crude nitrobenzene. Atthe same time, the acidic, alkaline and neutral wash water pathway wasstopped by switching off the respective pumps. The time taken was 5minutes.

Then the distillation was shut down by interrupting the feed of crudenitrobenzene and taking away the steam to the distillation column.Immediately thereafter, the product discharge was interrupted byswitching off the bottoms pump and the return stream at the top of thecolumn was stopped by stopping the benzene pump. After the vacuum pumphad been switched off and vented with nitrogen, the distillation was atrest. The time taken was 5 minutes.

Lastly, the alkaline wastewater workup was shut down by setting thethermal pressure decomposition to circulation mode and stopping thesteam to the pressure decomposition. At the same time, the supply andremoval of the alkaline wastewater to and from the stripper was stoppedby switching off the wastewater pumps and stopping the steam to thestripper. The time taken was 5 minutes. The circulation mode of thethermal pressure decomposition (TDZ) was stopped after 10 hours, as soonas the circulation water had been cooled below 100° C.

The complete stoppage took a total of two hours without purging andemptying of the apparatuses, pumps and pipelines, neglecting therunning-down of the TDZ. In modern automated production plants, thenumber of personnel required for the running-down operation only plays aminor role.

Procedure for the Cleaning Measure:

It was necessary to clear a blockage in the benzene preheater in thefeed of the crude nitrobenzene from the phase separation apparatus tothe crude nitro tank: First of all, the level in the phase separationvessel was lowered by 50%, in order that no further organic materialcould run into the benzene preheater to be cleaned. Subsequently, thebenzene preheater was purged with condensate through a purging stubmounted between the phase separation apparatus and benzene preheater for1 hour, in order to remove crude nitrobenzene and traces of sulfuricacid. The purge condensate was led off to the acidic wash. Thereafter,the benzene preheater was mechanically divided from the inlet andoutlet, and black precipitates in the benzene preheater that constitutedthe blockage were rinsed out with large amounts of condensate using twofurther purging stubs to the water treatment plant. The time taken was 3hours. After all 3 purging stubs had been disassembled, the inlet andoutlet of the benzene preheater were mounted. The time taken for thiswas 2 hours. Thereafter, the pipelines affected were heated up andcooled down several times, in the course of which the flange connectionswere re-tightened with the new seals. The time taken was 2 hours.

The cleaning measure took a total of 8 hours. In modern automatedproduction plants, the number of personnel required for the preparationfor the cleaning measure, namely partial emptying of the plant, mountingof the purging stub for preliminary cleaning of the benzene preheaterwith inlet and outlet and subsequent preliminary cleaning withcondensate, plays an important role. In this case, one additionalproduction worker is required. Workmen for the disassembly and assemblyof the pipelines for the cleaning measure and the cleaning personnelthemselves are likewise required.

Procedure for the Restarting of the Plant:

The vacuum pumps in the entire production plant were put in operationbeforehand. The phase separation apparatus and the cleaned benzenepreheater were inertized with 100 m³ (STP) of nitrogen.

Firstly, the washes were started by starting the crude nitrobenzene pumpto put the crude nitrobenzene supply from the crude nitrobenzene tank tothe acidic wash into operation. Thereafter, the acidic, alkaline andneutral wash water pathway was started by switching on the respectivepumps. Then the crude nitrobenzene pathway through the acidic, alkalineand neutral wash was started by switching on the delivery pumps for thecrude nitrobenzene upstream of the respective washes. The washingapparatuses that were filled with crude nitrobenzene and wash water wereat 45° C. and warmed gradually back up to 48° C. after the productionplant had been started.

Once the last stage of the neutral wash had been put in operation byfeeding in 3 t/h of condensate, the distillation was started by applyingvacuum to the distillation column and running crude nitrobenzene at 45°C. from the last neutral wash to the distillation column. Thereafter,the bottoms pump of the column was started and crude nitrobenzene wasrun to the crude nitrobenzene tank. Then the distillation column wassupplied with 2 t/h of 16 bar steam and heated up to 170° C. At 50° C.at the top of the column, the reflux was put in operation by startingthe benzene pump. The washes and the distillation were ready forrestarting of the production plant after 4.5 hours.

In parallel to the washes and the distillation, the acid water workupwas started by applying 1 t/h of 6 bar steam to heat up the acid waterstripper and starting the bottoms pump of the stripper. Subsequently,the feeding of the acidic wastewater from the acid water reservoir tankto the acid water stripper was started. Then the acid water workup wasready for restarting of the production plant. The time taken to startthe acid water stripper including the analysis of the acidic wastewaterfor organics by means of gas chromatography was 1 hour.

In parallel to the washes and the distillation, the alkaline wastewaterworkup was started by supplying thermal pressure decomposition which hadbeen put in circulation mode with 0.6 t/h of 110 bar steam, in order tobring the circulation water from 85° C. to 285° C. 2 hours prior to thedischarge of the alkaline wastewater, the stripper was supplied with 0.5t/h of 6 bar steam and the inlet and outlet of the alkaline wastewaterto and from the stripper were started by starting the wastewater pumps.The time taken was 8 hours.

One and a half hours before the washes and distillation were ready forrestarting of the production plant and after the acid water workup wasrunning in circulation mode, the sulfuric acid circulation pump wasstarted and the sulfuric acid was run in circulation through thenitrator, phase separation apparatus, flash evaporator and sulfuric acidreservoir tank. In the flash evaporator, the vacuum was started and then2.4 t/h of 6 bar steam were applied, which heated the circulatingsulfuric acid to starting temperature. This operation took 1 hour untilthe circulating sulfuric acid cooled down to 93° C. had been heated upto 100° C.

After 4.5 hours, the washes and the distillation were ready foroperation and the production plant was started by starting the benzeneand nitric acid pumps with 50% of the nameplate capacity, whichcorresponded to a production output of 25 t/h of nitrobenzene. After 1minute, the reaction product arrived in the phase separation apparatusand the acid water stripper was set to discharge of the acidicwastewater and the bottoms column of the distillation was set to productdischarge of the nitrobenzene end product. The running of the productionplant up to nameplate load, which is automated in a modern productionplant, takes another 1 hour.

Assessment of the Energy and Auxiliaries Required and Time Taken for theRunning Down and Starting Up of the Plant Including the CleaningMeasure:

The total time taken for the measure was 15 hours. This applies ifsufficient personnel is available and no technical difficulties occur.The time taken for the cleaning itself was 8 hours. For the shutdown,2.5 hours were required. The startup took 4.5 hours.

Thus, a total of 775 tonnes of nitrobenzene production was lost. Thesteam consumption was 4.4 tonnes of 6 bar steam, 8 tonnes of 16 barsteam and 4.8 tonnes of 110 bar steam. In the running down of the plantand during the measure, no steam was consumed. The consumption ofnitrogen for the running down was 550 m³ (STP) and for the restart ofthe plant was 100 m³ (STP). The consumption of condensate was 15.5 m³ (2m³ for the purging of the heat exchanger and 13.5 m³ for the startup ofthe neutral wash). The consumption of power totaled 6130 kW. For therunning down of the plant, 1100 kW were required for the TDZ, 180 kW forthe nitration and 445 kW for the washes. For the startup of the plant,4005 kW were required for the washes and 400 kW for the circulatingsulfuric acid pumps. During the cleaning measure, no power was consumed.

Example 2 (Inventive): Brief Shutdown of the Production Plant withCirculation Mode in the Plant Sections Unaffected by the CleaningMeasure, Cleaning Measure and Restarting of the Plant

The brief shutdown of the plant served for cleaning operations in thenitration region. For this purpose, the nitration region was run downcompletely and the other plant sections such as the washes, thedistillation, and the acidic and alkaline wastewater workup were put incirculation mode. The energy supplies during the cleaning operationswere switched off only in the nitration region (the vacuum remained onstandby). After the cleaning operations, the plant was started up again,for which it was necessary to completely inertize, fill and heat up onlythe nitration region.

Procedure for the Complete Stoppage of the Nitration and Adjustment ofthe Remaining Plant Sections to Circulation Mode:

Firstly, the acid water workup was put in circulation mode by switchingthe discharge of the acidic wastewater into the wastewater channel backinto the acid water reservoir tank by means of the bottoms pump of thestripper, which requires 10 kW/h. The steam to the acid water stripperwas throttled from 1.2 t/h to 0.7 t/h of 6 bar steam and the feed ofacid water from the acid water reservoir tank by means of the acid waterpump, which requires 10 kW/h, into the acid water stripper was reducedfrom 20 m³ to 13 m³. The changeover of the acid water workup tocirculation mode took place within 33 seconds by means of automation.

Next, the alkaline wastewater workup was put in circulation mode byswitching the discharge of the alkaline wastewater of the thermalpressure decomposition (TDZ) into the wastewater channel back into thealkaline wastewater reservoir by means of the high-pressure pump of theTDZ, which requires 55 kW/h. The steam to the pressure decomposition wasthrottled from 0.32 t/h to 0.20 t/h of 110 bar steam and the feed ofalkaline wastewater from the alkaline wastewater reservoir into the TDZwas reduced from 4.0 m³/h to 2.5 m³/h. The changeover of the TDZ tocirculation mode took place within 5 minutes by means of automation,because the reduction of the feed to the TDZ was effected manually.

At the same time, the stripper of the alkaline wastewater was put incirculation mode by interrupting the discharge of the alkalinewastewater into the TDZ and switching the alkaline wastewater back tothe wastewater tank by means of the bottoms pump of the stripper, whichrequires 10 kW/h. The steam to the stripper for the alkaline wastewaterwas throttled from 0.4 t/h to 0.25 t/h of 6 bar steam, and the feed ofalkaline wastewater from the wastewater tank into the stripper for thealkaline wastewater was reduced from 4 m³ to 2.5 m³ by means of theinjection pump for the alkaline wastewater, which requires 10 kW/h. Thechangeover of the stripper for the alkaline wastewater to circulationmode took place within 27 seconds by means of automation.

Next, the washes and the distillation were put in circulation mode byswitching the discharge of the nitrobenzene end product from thenitrobenzene column to the nitrobenzene storage tank over to the crudenitrobenzene tank by means of the bottoms pump of the column, whichrequires 24 kW/h. At the same time, the benzene-containing organic phaseof the vapor phase separation apparatus was guided by means of naturalefflux to the crude nitrobenzene tank. The aqueous phase of the vaporphase separation apparatus was disposed of via the acidic wash and theacidic wastewater workup. The vacuum system of the nitrobenzene columnremained in operation. The circulation mode was established by runningthe contents of the crude nitrobenzene tank by means of delivery pumpsthrough all the washes back to the nitrobenzene column. The crude nitrotank, the acidic wash, the alkaline wash and the 3 neutral washes eachhave a delivery pump, each of which requires 24 kW/h. The feed of crudenitrobenzene into the washes or distillation was reduced from 42 t/h to27 t/h. The steam to the nitrobenzene column was throttled from 2.5 t/hto 1.6 t/h of 16 bar steam. The wash water for the neutral wash wasreduced from 6.3 m³/h to 4.0 m³/h. The changeover of the washes and thedistillation to circulation mode took place within 5 minutes by means ofautomation.

Lastly, the nitration was shut down by switching off the metering pumpsfor the input streams of benzene and nitric acid. The vapor from theflash evaporator was stopped 5 minutes after the benzene and nitric acidraw materials. The circulation of sulfuric acid continued for 1 houruntil all organics were discharged from the nitration circuit consistingof nitrators, phase separation apparatus, flash evaporator andcirculating sulfuric acid reservoir tank. Then the circulation ofsulfuric acid at 100° C. was interrupted by switching off thecirculation pump. The nitrators, the phase separation apparatus and theflash evaporator were left under standing sulfuric acid. The remainingcirculating sulfuric acid was in the sulfuric acid reservoir tank.Simultaneously with the circulation pump, the vacuum pump to the flashevaporator was shut down and the vacuum was broken with 350 m³ (STP) ofnitrogen. The nitration circuit was then at rest. The time taken for theshutdown was 2 hours.

The preparation (establishing circulation mode of washing, distillation,alkaline and acidic wastewater and the shutdown of the nitration) forthe cleaning measure took a total of 2 hours and 11 minutes withoutpurging and emptying of the apparatuses, pumps and pipelines.

Procedure for the Cleaning Measure:

The cleaning measure was conducted as described in example 1.

Procedure for the Restarting of the Plant:

The vacuum pump for the flash evaporator was put in operationbeforehand. The phase separation apparatus and the cleaned benzenepreheater were inertized with 100 m³ (STP) of nitrogen. The startup ofthe plant was started with the starting of the nitration, by startingthe sulfuric acid circulation pump and running the sulfuric acid incirculation through the nitrator, phase separation apparatus, flashevaporator and sulfuric acid reservoir tank. In the flash evaporator,the vacuum had already been started, and then 2.4 t/h of 6 bar steamwere applied, which heated the circulating sulfuric acid to startingtemperature. This operation took 1 hour until the circulating sulfuricacid cooled down to 93° C. had been heated up to 100° C. Then thenitration was started by starting the benzene and nitric acid pumps at50% of the nameplate capacity, which corresponded to a production outputof 25 t/h of nitrobenzene. After 1 minute, the reaction product arrivedin the phase separation apparatus, the acid water stripper was set todischarge of the acidic wastewater and the bottoms column of thedistillation was set to product discharge of the nitrobenzene endproduct. At the same time, the stripper for the alkaline wastewaterworkup was switched to discharge to the TDZ, and the TDZ was switchedfrom circulation mode to discharge into the wastewater channel. Therunning of the production plant up to nameplate load, which is automatedin a modern production plant, took another 1 hour.

Assessment of the Energy Required and Time Taken for the Running Downand Starting Up of the Plant from Circulation Mode, Including theCleaning Measure:

The total time taken for the measure was 11 hours and 12 minutes. Thisapplies particularly if sufficient personnel is available and notechnical difficulties occur. The time taken for the cleaning itself was8 hours. The running down into circulation mode took 2 hours and 11minutes. The startup from circulation mode took 1 hour and 1 minute.

In this way, a total of 585 tonnes of nitrobenzene production was lost.The steam consumption was 12 tonnes of 6 bar steam, 13 tonnes of 16 barsteam and 1.6 tonnes of 110 bar steam for the circulation mode. In therunning down of the plant into circulation mode, no steam was consumed.The consumption of nitrogen for the running down into circulation modewas 350 m³ (STP) and for the restart of the plant from circulation modewas 100 m³ (STP). The consumption of condensate for the measure was 47m³ (2 m³ for the purging of the heat exchanger and 45 m³ for the runningdown and startup and circulation mode of the washes). The consumption ofpower totaled 8525 kW. The running down of the plant consumed 1943 kW,the circulation mode during the cleaning measure consumed 5680 kW forthe circulation mode and the startup of the plant consumed 905 kW ofpower.

Conclusion for the Complete Stoppage (Comparative Example 1) VersusCirculation Mode (Example 2) for the Cleaning Measure:

As a conclusion for the complete stoppage (comparative example 1) versuscirculation mode (example 2), it can be stated that the extra demand forpower and condensate is more than compensated for by the lowerconsumption of nitrogen, but particularly by the higher availability ofthe plant, which is manifested by a higher production output. The steamconsumption is about the same. The time saved for the cleaning measureis 3 hours and 48 minutes, which corresponds to an improved productionoutput of 190 tonnes of nitrobenzene.

Example 3 (Comparative Example): Brief Shutdown of the Production Plantwith Complete Stoppage of the Plant, Repair Measure and Restarting ofthe Plant Brief Shutdown of the Plant for a Repair Measure in theWashing Operation

For this purpose, the plant was run down completely, i.e. nitration,washes and distillation. The energy supplies were switched off duringthe repair measure. After the repair, the plant was started up again,for which it was necessary to inertize, fill and heat the entire plant.

Procedure for the Complete Stoppage of the Plant:

The plant was shut down as described in example 1. The complete stoppageagain took two hours without purging and emptying of the apparatuses,pumps and pipelines, neglecting the running-down of the TDZ.

Procedure for the Repair Measure:

Sealing of leaky pipeline in the neutral wash: For this purpose, thepipeline affected in the downstream washing apparatus was blown clearwith 10 m³ of nitrogen. Then the pipeline was purged with 2 m³ ofcondensate and emptied. Subsequently, the failed seal in the pipelinewas replaced. The repair measure took a total of 1.5 hours. In modernautomated production plants, the number of personnel required for thepreparation for the repair, namely the purging of the pipeline, plays animportant role. In this case, one additional production worker isrequired. Workmen for disassembly and assembly of the pipeline in orderto replace the failed seal are likewise required.

Procedure for the Restarting of the Plant:

The vacuum pumps in the entire production plant were put in operationbeforehand.

Subsequently, the plant was restarted as described in example 1. Theplant had been started up again after 4.5 hours and could be run up tonameplate load.

Assessment of the Energy Required and Time Taken for the Running Downand Starting Up of the Plant, Including the Cleaning Measure:

The total time taken for the measure was 8.5 hours, since sufficientpersonnel were available and no technical difficulties occurred. Thetime taken for the repair itself was 1.5 hours. For the shutdown, 2.5hours were required. The startup took 4.5 hours. Thus, a total of 450tonnes of nitrobenzene production was lost. The steam consumption was3.4 tonnes of 6 bar steam and 8 tonnes of 16 bar steam and 4.8 tonnes of110 bar steam. In the running down of the plant, no steam was consumed.A total of 610 m³ (STP) of nitrogen were required, of which 550 m³ (STP)was for the running-down and 50 m³ (STP) for the restarting of theplant, and a further 10 m³ (STP) for the repair measure.

The consumption of condensate was 15.5 m³ (2 m³ for the purging of thepipeline and 13.5 m³ for the startup of the neutral wash). Theconsumption of power totalled 5470 kW. For the running down of theplant, 440 kW were required for the TDZ, 180 kW for the nitration and445 kW for the washes. For the startup of the plant, 4005 kW wererequired for the washes and 400 kW for the circulating sulfuric acidpumps. During the repair measure, no power was consumed.

Example 4 (Inventive): Brief Shutdown of the Production Plant withCirculation Mode in the Plant Sections Unaffected by the Repair Measure,Repair Measure and Restarting of the Plant

Brief shutdown of the plant for repair operations in the nitrobenzenewash: For this purpose, the washes and distillation were run downcompletely. The other plant sections such as the nitration and theacidic and alkaline wastewater workup were put in circulation mode. Theenergy supplies during the repair operations were switched off only inthe wash and the distillation (vacuum remained on standby). After therepair, the plant was restarted.

Procedure for the Complete Stoppage of the Washes and Distillation andAdjustment of the Remaining Plant Sections to Circulation Mode:

Firstly, the acid water workup was put in circulation mode by switchingthe discharge of the acidic wastewater into the wastewater channel backinto the acid water reservoir tank by means of the bottoms pump of thestripper, which requires 10 kW/h. The steam to the acid water stripperwas throttled from 1.2 t/h to 0.7 t/h of 6 bar steam and the feed ofacid water from the acid water reservoir tank by means of the acid waterpump, which requires 10 kW/h, into the acid water stripper was reducedfrom 20 m³ to 13 m³. The changeover of the acid water workup tocirculation mode took place within 29 seconds by means of automation.

Next, the alkaline wastewater workup was put in circulation mode byswitching the discharge of the alkaline wastewater of the thermalpressure decomposition (TDZ) into the wastewater channel back into thealkaline wastewater reservoir by means of the high-pressure pump of theTDZ, which requires 55 kW/h. The steam to the pressure decomposition wasthrottled from 0.32 t/h to 0.20 t/h of 110 bar steam and the feed ofalkaline wastewater from the alkaline wastewater reservoir into the TDZwas reduced from 4.0 m³/h to 2.5 m³/h. The changeover of the TDZ tocirculation mode took place within 5 minutes by means of automation,because the reduction of the feed to the TDZ was effected manually.

At the same time, the stripper of the alkaline wastewater was put incirculation mode by interrupting the discharge of the alkalinewastewater into the TDZ and switching the alkaline wastewater back tothe wastewater tank by means of the bottoms pump of the stripper, whichrequires 10 kW/h. The steam to the stripper for the alkaline wastewaterwas throttled from 0.4 t/h to 0.25 t/h of 6 bar steam, and the feed ofalkaline wastewater from the wastewater tank into the stripper for thealkaline wastewater was reduced from 4 m³ to 2.5 m³ by means of theinjection pump for the alkaline wastewater, which requires 10 kW/h. Thechangeover of the stripper for the alkaline wastewater to circulationmode took place within 31 seconds by means of automation.

Next, the feedstocks to the nitration were stopped. The metering pumpsfor the input streams of benzene and nitric acid were switched off. Thecirculating sulfuric acid continued to circulate at 100° C. through thenitrators, the phase separation apparatus, flash evaporator andcirculating sulfuric acid reservoir tank. The flash evaporator required0.3 t/h of 6 bar steam. The time taken was 1 minute.

Lastly, the washes were shut down by interrupting the crude nitrobenzenefeed from the crude nitrobenzene tank to the acidic wash. The crudenitrobenzene pathway through the acidic, alkaline and neutral wash wasstopped by stopping the delivery pumps for the crude nitrobenzeneupstream of the respective washes. The washes were at 48° C. andremained filled with crude nitrobenzene. At the same time, the acidic,alkaline and neutral wash water pathway was stopped by switching off therespective pumps. The time taken was 5 minutes.

Then the distillation was shut down by interrupting the feed of crudenitrobenzene and taking away the steam to the distillation column.Immediately thereafter, the product discharge was interrupted byswitching off the bottoms pump and the return stream at the top of thecolumn was stopped by stopping the benzene pump. The vacuum pumpcontinued to run. The time taken was 5 minutes.

The preparation (establishment of circulation mode in the nitration andthe alkaline and acidic wastewater workup and the shutdown of the washesand distillation) for the repair measure took a total of 11 minuteswithout purging and emptying of the apparatuses, pumps and pipelines.

Procedure for the Repair Measure:

The repair measure was conducted as described in example 3. The timetaken was again 1.5 hours. The steam consumption during circulation modewas 1.6 tonnes of 6 bar steam and 0.4 tonne of 110 bar steam. 400 kW ofpower were required for the operation of the vacuum pump and sulfuricacid circulation pump during circulation mode.

Procedure for the Restarting of the Plant:

Firstly, the washes were started by starting the crude nitrobenzene pumpto put the crude nitrobenzene supply from the crude nitrobenzene tank tothe acidic wash into operation. Thereafter, the acidic, alkaline andneutral wash water pathway was started by switching on the respectivepumps. Then the crude nitrobenzene pathway through the acidic, alkalineand neutral wash was started by switching on the delivery pumps for thecrude nitrobenzene upstream of the respective washes. The washingapparatuses that were filled with crude nitrobenzene and wash water wereat 45° C. and were gradually warmed back up to 48° C. after theproduction plant had been started.

Once the last stage of the neutral wash had been put in operation byfeeding in 3 t/h of condensate, the distillation was started by runningcrude nitrobenzene at 45° C. from the last neutral wash to thedistillation column. Thereafter, the bottoms pump of the column wasstarted and crude nitrobenzene was run to the crude nitrobenzene tank.Then the distillation column was supplied with 2 t/h of 16 bar steam andheated up to 170° C. At 50° C. at the top of the column, the reflux wasput in operation by starting the benzene pump. The washes and thedistillation were ready for restarting of the production plant after 1hour.

Then the nitration was started by starting the benzene and nitric acidpumps at 50% of the nameplate capacity, which corresponded to aproduction output of 25 t/h of nitrobenzene. After 1 minute, thereaction product arrived in the phase separation apparatus, the acidwater stripper was set to discharge of the acidic wastewater and thebottoms column of the distillation was set to product discharge of thenitrobenzene end product. At the same time, the stripper for thealkaline wastewater workup was switched to discharge to the TDZ, and theTDZ was switched from circulation mode to discharge into the wastewaterchannel. The running-up of the production plant to nameplate load tookanother 1 hour.

Assessment of the Energy Required and Time Taken for the Running Downand Starting Up of the Plant from Circulation Mode, Including the RepairMeasure:

The total time taken for the measure was 3 hours and 41 minutes. Thetime taken for the repair itself was 1.5 hours. The running down intocirculation mode took 11 minutes. The startup from circulation mode took1 hour and 1 minute.

Thus, a total of 165 tonnes of nitrobenzene production was lost. Thesteam consumption was 1.6 tonnes of 6 bar steam, 2 tonnes of 16 barsteam and 0.8 tonne of 110 bar steam. In the running down of the plantinto circulation mode, no steam was consumed. 10 m³ (STP) of nitrogenwere required for the repair measure and 50 m³ (STP) of nitrogen for therestarting of the plant. The consumption of condensate was 7 m³ (2 m³for the purging of the pipeline and 5 m³ for the running-down andstartup of the neutral wash). The consumption of power totaled 1593 kW.The running-down of the plant consumed 178 kW for the running-down ofthe nitration into circulation mode, 510 kW for the circulation modeduring the cleaning measure and 905 kW of power for the startup of theplant.

Conclusion for the Complete Stoppage (Comparative Example 3) VersusCirculation Mode (Example 4) for the Repair Measure:

As a conclusion for the complete stoppage (comparative example 3) versuscirculation mode (example 4), it can be stated that smaller amounts ofsteam, power, nitrogen and condensate were consumed in circulation modeand, on top of that, the availability of the plant, which is manifestedby a higher production output, was distinctly better. The time saved forthe repair measure was 5 hours and 48 minutes, which corresponds to animproved production output of 290 tonnes of nitrobenzene.

The invention claimed is:
 1. A process for preparing nitrobenzene,comprising (I) nitrating benzene with nitric acid in sulfuric acid toform nitrobenzene in a reactor, with introduction of a mass flow ofbenzene (m₁), a mass flow of nitric acid (m₂), and a mass flow ofsulfuric acid (m₃), into the reactor, thereby obtaining a reactionmixture comprising an organic nitrobenzene-containing phase and anaqueous sulfuric acid-containing phase; (II) separating the organicnitrobenzene-containing phase and the aqueous sulfuric acid-containingphases of the reaction mixture from (I) in a phase separation apparatus;and optionally (III) to (VII): (III) concentrating the aqueous sulfuricacid-containing phase separated in (II) by evaporating water in anevaporation apparatus to give an aqueous sulfuric acid-containing phasehaving elevated sulfuric acid concentration, with recycling of theconcentrated sulfuric acid-containing aqueous phase via a sulfuric acidtank into (I) and use thereof as a constituent of the mass flow m₃; (IV)washing the organic nitrobenzene-containing phase obtained in (II) in atleast two stages and separating off an aqueous phase after each stage,using a wash vessel having a phase separation unit or a wash vessel anda separate phase separation apparatus in each stage, (V) distilling theorganic nitrobenzene-containing phase obtained in the last stage of (IV)in a distillation apparatus, and (VI) working up the aqueous phase fromthe first wash stage of (IV), comprising collecting the aqueous phase ina wastewater collection vessel and cleaning said aqueous phase in anapparatus for distillation or stripping, and (VII) working up theaqueous phase from the second wash stage of the at least two wash stagesof (IV), comprising collecting the aqueous phase in a wastewatercollection vessel and cleaning said aqueous phase in an apparatus fordistillation or stripping, where the apparatus for distillation orstripping may be connected up- and/or downstream of an apparatus forthermal pressure decomposition, wherein the process is interrupted, theinterruption comprising the steps of shutting down one or more, but notall, plant sections from (I) to (VII), reducing the mass flow m₁ and themass flow m₂ to zero and, in at least one of the plant sections that hasnot been shut down, using an output stream of said at least one plantsection that has not been shut down as an input stream for therespective plant section or an upstream plant section, thereby operatingsaid at least one plant section that has not been shut down incirculation mode.
 2. The process as claimed in claim 1, additionallycomprising (III) to (VII).
 3. The process as claimed in claim 2, wherein(IV) comprises (IVa) washing the organic nitrobenzene-containing phaseobtained in (II) in at least one wash stage, and separating phases intoa first aqueous phase and a first organic nitrobenzene-containing phase,(IVb) washing the first organic nitrobenzene-containing phase obtainedin (IVa) in at least one alkaline wash with an aqueous solution of abase selected from the group consisting of sodium hydroxide, sodiumcarbonate and sodium hydrogencarbonate, and separating phases into asecond aqueous phase and a second organic nitrobenzene-containing phase,and (IVc) washing the second organic nitrobenzene-containing phaseobtained in (IVb) in at least one neutral wash with water, andseparating phases into a third aqueous phase and a third organicnitrobenzene-containing phase.
 4. The process as claimed in claim 1,wherein an output stream in every plant section that has not been shutdown is used again as an input stream for the corresponding plantsection or an upstream plant section.
 5. The process as claimed in claim2, wherein an output stream from the plant section from (V) is used asan input stream for the plant section from (IV).
 6. The process of claim1, additionally comprising (1) at least one of: (a) conducting aninspection, repair, cleaning or maintenance measure in the one or moreplant sections that have been shut down, and (b) compensating for a lackof feedstocks or auxiliaries, during the interruption of the process;and (2) restarting the process again after completion of saidinspection, repair, cleaning or maintenance measure, or after the lackof feedstocks or auxiliaries has been overcome.